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CN1196002A - Oil-water emulsifiers - Google Patents

Oil-water emulsifiers Download PDF

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Publication number
CN1196002A
CN1196002A CN96196886A CN96196886A CN1196002A CN 1196002 A CN1196002 A CN 1196002A CN 96196886 A CN96196886 A CN 96196886A CN 96196886 A CN96196886 A CN 96196886A CN 1196002 A CN1196002 A CN 1196002A
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Prior art keywords
alkyl
acid
water emulsifiers
formula
described oil
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CN96196886A
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CN1092995C (en
Inventor
阿基姆·安斯曼
罗尔夫·卡瓦
赫尔加·冈德克
约瑟夫·凯斯特
安妮特·施瓦茨
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BASF Personal Care and Nutrition GmbH
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Henkel AG and Co KGaA
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/39Derivatives containing from 2 to 10 oxyalkylene groups
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/02Cosmetics or similar toiletry preparations characterised by special physical form
    • A61K8/04Dispersions; Emulsions
    • A61K8/06Emulsions
    • A61K8/062Oil-in-water emulsions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/33Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
    • A61K8/37Esters of carboxylic acids
    • A61K8/375Esters of carboxylic acids the alcohol moiety containing more than one hydroxy group
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/40Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
    • A61K8/42Amides
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00Cosmetics or similar toiletry preparations
    • A61K8/18Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/60Sugars; Derivatives thereof
    • A61K8/604Alkylpolyglycosides; Derivatives thereof, e.g. esters
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61QSPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q19/00Preparations for care of the skin
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/017Mixtures of compounds
    • C09K23/018Mixtures of two or more different organic oxygen-containing compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/22Amides or hydrazides
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/28Aminocarboxylic acids
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/34Higher-molecular-weight carboxylic acid esters
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09KMATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/56Glucosides; Mucilage; Saponins
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10STECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/905Agent composition per se for colloid system making or stabilizing, e.g. foaming, emulsifying, dispersing, or gelling
    • Y10S516/914The agent contains organic compound containing nitrogen, except if present solely as NH4+
    • Y10S516/915The compound contains -C[=O]NHH where substitution may be made for the hydrogen

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  • Health & Medical Sciences (AREA)
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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Dispersion Chemistry (AREA)
  • Dermatology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Molecular Biology (AREA)
  • Cosmetics (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Medicinal Preparation (AREA)
  • Fats And Perfumes (AREA)
  • Medicines Containing Plant Substances (AREA)

Abstract

The proposal is for novel liquid and easily pumped oil-water emulsifiers containing a1) alkyl and/or alkenyl oligoglycosides, a2) fatty acid-N-alkyl polyhydroxy alkyl amides and/or a3) acyl glutamates and b) polyol polyhydroxy stearates, with the proviso that the proportion by weights of a) : b) is in the range from 90 : 10 to 10 : 90.

Description

Oil-water emulsifiers
FIELD OF THE INVENTION
The present invention relates to new contain selected oil-water emulsifiers that surfactant and particular polymers made up and the application in preparation cosmetics or pharmaceutical preparation thereof.
Background technology
The polyglycereol numb carboxylic esters of combing known already as emulsifying agent more, can be used for forming low viscosity emulsion [referring to EP-A10559013 (Th.Goldschmidt), EP-A10440203 (Lotte Co.) and WO85/04346 (Meiji Milk Prods.)].Yet, proved that commercially available polyglycereol, and the numb carboxylic ester of combing can not form emulsions with all oil commonly used in the cosmetics more already, and can only form emulsions with in the particular polarity scope those; And the storage-stable of these emulsions is also limited.Its major defect at first is, common commercially available prod can not sufficiently be stablized and contained for example emulsion of vegetable oil of strong polar oil.But and consider that from the ecology endurance such emulsion market exactly is needed.
European patent specification EP-B10553241 (SEPPIC) discloses a kind of alkyl poly glucoside of respective chain length and self-emulsifying mixtures of fatty alcohol of containing equally.Yet, when using such emulsifying agent, can see the change of undesirable viscosity in many cases along with the resting period.
Task of the present invention is, the oil-water emulsifiers of new no oxirane is provided, and they can form stable in storage emulsion with diversified oil body.
Summary of the invention
Theme of the present invention is an oil-water emulsifiers, contains
A1) alkyl and/or alkenyl oligoglycosides,
A2) aliphatic acid-N-alkyl polyhydroxy alkylamide and/or
A3) acyl glutamic acid ester
B) polyalcohol multi-hydroxy stearic acid ester,
Its condition is, a): weight ratio b) is 90: 10 to 10: 90, preferred 70: 30 to 30: 70, and particularly 60: 40 to 40: 60.
Find beyond expectationly, use described surfactant to be preferably C 12/14Alkyl oligoglycosides and polyalcohol multi-hydroxy stearic acid ester, preferably with polyglycereol poly--mixture of 12-hydroxy stearic acid ester is as oil-water emulsifiers, the emulsion that obtains can stably be stored, even also be not subjected to the polarity effect of used oil body when variations in temperature.The present invention also recognizes, particularly works as and uses at least a polyalcohol, and preferably glycerine, during as supplementary element, this mixture is liquid, and is easy to pumping.Alkyl and/or alkenyl oligoglycosides
Alkyl and/or alkenyl oligoglycosides are known non-ionic surface active agents, and its molecular formula is as shown in the formula (I)
R 1O-[G] p(I) R in the formula 1Expression contains the alkyl and/or the alkenyl of 4-22 carbon atom, and G represents to contain the glycosyl of 5 or 6 carbon atoms, and p is numerical value 1-10.They can obtain with the method for preparative organic chemistry.As the representative of many documents, only mention EP-A1-0301298 and WO90/03977 here.
Alkyl and/or alkenyl oligoglycosides can be by the aldose or the ketoses of 5 or 6 carbon atoms, preferred glucose, and obtain.Therefore, preferred alkyl and/or alkenyl oligoglycosides are alkyl and/or alkenyl oligomeric glucopyranoside.
Index p in the general formula (I) represents oligomeric degree (DP-degree), that is to say the distribution of monoglycosides and oligoglycosides, and its numerical value is 1-10.P integer always in given compound at first can suppose p=1-6, and this numerical value p is the calculated value that analytic approach obtains for specific alkyl oligoglycosides, and it is a mark normally.Preferred alkyl and/or the alkenyl oligoglycosides that uses average oligomeric degree p as 1.1-3.0.From application point, the oligomeric degree of preferred alkyl that uses and/or alkenyl oligoglycosides is less than 1.7, especially between 1.2 and 1.4.
Alkyl or alkenyl R 1Can be by 4-11, the primary alconol of preferred 8-10 carbon atom obtains.Typical example is butanols, hexanol, octanol, decyl alcohol and undecylenic alcohol and cuts thereof, resulting cuts during for example at the commercial fatty acids methyl ester hydrogenation or by the synthetic aldehyde hydrogenation of Reolen carbonyl.Preferably, chain length is C 8-C 10(DP=1-3) alkyl oligoglycosides, they are at separated technical grade C 8-C 18Form as first runnings during-coconut fatty alcohol, can contain C less than 6% (weight) 12-alcohol is as impurity, also preferably based on the C of industry 9/11The alkyl oligoglycosides of-oxo-alcohols (DP=1-3).
Alkyl or alkenyl R 1Also can be by 12-22, the primary alconol of preferred 12-14 carbon atom obtains.Typical example is laruyl alcohol, myristyl alcohol, cetanol, Palmitoleyl alcohol, stearyl alcohol, isooctadecanol, oleyl alcohol, anti-oleyl alcohol, petroselinum alcohol, arachidic alcohol, suitable-the 9-gadoleyl alcohol, docosyl alcohol, erucyl alcohol, Brazilian enol and cuts thereof, and they can obtain as mentioned above.Preferably be the C of 1 to 3 hydrogenation based on DP 12/14The alkyl oligoglycosides of-coconut alcohol.Aliphatic acid-N-alkyl polyhydroxy alkylamide aliphatic acid-N-alkyl polyhydroxy alkylamide is a non-ionic surface active agent, by formula (II) expression,
Figure A9619688600061
R in the formula 2CO represents the aliphatic acyl of 6-22 carbon atom, R 3The alkyl or the hydroxy alkyl of expression hydrogen, a 1-4 carbon atom, [Z] expression contains the polyhydroxy alkyl of the straight or branched of 3-12 carbon atom and 3-10 hydroxyl.
This aliphatic acid-N-alkyl polyhydroxy alkylamide is known material, can obtain by carrying out a kind of reducing sugar of reductive amination with ammonia, alkylamine or alkanolamine and then carry out acidylate with a kind of aliphatic acid, fatty acid alkyl esters or a kind of aliphatic acid chlorination thing usually.Its preparation method is described in US patent documentation US1985424, US2016962 and US2703798 and International Patent Application WO 92/06984.One piece of summary of this theme is published in Tens.Surf.Det.25 by H.Kelkenberg, in 8 (1988).This aliphatic acid-N-alkyl polyhydroxy alkylamide is preferably obtained by the reducing sugar that contains 5 or 6 carbon atoms, is particularly obtained by glucose.It is preferred that aliphatic acid-N-alkyl polyhydroxy alkylamide is suc as formula (III) described aliphatic acid-N-alkyl glucose amide:
Figure A9619688600062
The glucamide of preferred use formula (III) is as aliphatic acid-N-alkyl polyhydroxy alkylamide, wherein R 3Be hydrogen or alkyl, R 2CO is acyl moiety or its cuts of caproic acid, sad, capric acid, laurate, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselic acid, linoleic acid, leukotrienes, arachidic acid, gadoleic acid, mountain Yu acid, savoy acid.The aliphatic acid of particularly preferred formula (III)-N-alkyl-glucamide is by also following with laurate or C with methyl amine amination glucose 12/14-coco-nut oil fatty acid or its corresponding derivative acidylate and obtain.In addition, also can obtain the polyhydroxy alkyl acid amides by maltose and phthalic acid sugar (Palatinose).
The application of aliphatic acid-N-alkyl polyhydroxy alkylamide also is the theme of many public publications.For example, European patent application EP-A-0285768 (Huels) discloses used as plasticizer.France prospectus FR-A-1580491 (Henkel) has described the aqueous cleaning agent composition based on sulfuric ester and/or sulphonic acid ester, non-ionic surface active agent and soap class in case of necessity, and it contains aliphatic acid-N-alkyl glucose amide as foam modifier.German patent specification DE-C14400632 (Henkel) has described the mixture of being made up of short chain and long-chain glucamide.Germany prospectus DE-A14236958 and DE-A14309567 (Henkel) have reported further that then the glucamide of longer alkyl is used as the false manifestation of vitality and makes up with protein hydrolysate and cationic surfactant and be used for hair products through acid amides and glucamide in skin care item.
International Patent Application WO 92/06153; WO92/06156; WO92/06157; WO92/06158; WO92/06159 and WO92/06160 (Procer﹠amp; Gamble) theme is the mixture of surfactant, ether carboxylic acid, ether sulfuric ester, sulfonic acid methyl ester and the non-ionic surface active agent of aliphatic acid-N-alkyl-glucamide and anion surfactant, sulfuric ester and/or sulphonic acid ester structure.The application of these materials in various washing agent, dishwasher detergent and cleaning agent is described in and asks WO92/06152 in the international monopoly; WO92/06154; WO92/06155; WO92/06161; WO92/06162; WO92/06164; WO92/06170; WO92/06171 and WO92/06172 (Procer﹠amp; Gamble) in.Acyl glutamic acid (salt)
Acyl glutamic acid (salt) is known anion surfactant, shown in formula (IV),
Figure A9619688600071
COR in the formula 4Expression contains the acyl group of the straight or branched of 6-22 carbon atom and 0 and/or 1,2 or 3 two key, and X represents hydrogen, alkali metal and/or alkaline-earth metal, ammonium, alkylammonium, alkanol ammonium or glucose ammonium.Its preparation example as, can finish by glutamic acid being carried out the Schotten-Baumann acidylate with aliphatic acid, fatty acid ester or aliphatic acid chlorination thing.The commercially available prod for example can be by HoechstAG, Frankfurt/DE or by Ajinomoto Co Inc., Tokyo/JP obtains.The preparation of acyl glutamic acid (salt) and the summary of character by publication such as M.Takehara at J.Am Oil.Chem.Soc, 49, on (1972).The representative instance of the admissible acyl glutamic acid of the present invention (salt) is by 6-22 carbon atom, the anion surfactant that the aliphatic acid of preferred 12-18 carbon atom obtains, for example C 12/14-or C 12/18-coconut fatty acid, laurate, myristic acid, palmitic acid and/or stearic acid.Preferred especially N coco group-sodium glutamate or N-coco group-potassium glutamate and N stearyl-L-sodium glutamate or N-stearyl-L-potassium glutamate.Polyalcohol multi-hydroxy stearic acid ester
Polyalcohol multi-hydroxy stearic acid ester is the ester of polyalcohol and multi-hydroxy stearic acid.The polyalcohol component for example can be obtained by glycerine, ethylene glycol, diethylene glycol, propane diols, polyglycereol, trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, pentaerythrite, dipentaerythritol, methyl and butyl glycoside, D-sorbite, mannitol, glucose, sucrose or aminoglucose.Respective substance for example can be by document GB-A1524782 or EP-A0000424 and is learnt.
Material component b) be preferably polyglycereol multi-hydroxy stearic acid ester, it can be obtained by following mode: making from condensation degree is 2-20, and the multi-hydroxy stearic acid of preferred 2-10 and the polyglycereol mixture (GC method) of following composition carry out esterification by known method:
Glycerine: 5-35 (15-30) % (weight)
Two glycerine: 15-40 (20-32) % (weight)
Triglycerin: 10-35 (15-25) % (weight)
Four glycerine: 5-20 (8-15) % (weight)
Five glycerine: 2-10 (3-8) % (weight)
Low polyglycereol: the numerical value that adds in 100% (weight) bracket is preferable range.The preparation of polyalcohol multi-hydroxy stearic acid ester can be undertaken by known manner.For polyglycereol multi-hydroxy stearic acid ester, preferably at first prepare polyglycereol, prepare multi-hydroxy stearic acid then, make both esterifications at last.The preparation of the polyglycereol of above-mentioned composition can be carried out from condensation under 200-260 ℃ temperature in the presence of appropriate catalyst such as the described potash of DE-A14029323 (Henkel), silicate or the described borate of DE-A14117033 (Henkel) by glycerine.The preparation example of multi-hydroxy stearic acid is as finishing by the preferred 12-hydroxy stearic acid of the polycondensation hydroxy stearic acid of base catalysis, and this hydroxy stearic acid obtains by the hydrogenation of castor oil acid or industrial Castor Oil Fatty Acid.Be preferably formed and contain 2-10, particularly the straight chain esterification products of a 2-8 aliphatic acid unit.Typically reach following distribution (GPC method):
Monomer: 1-10% (weight)
Dimer: 5-15% (weight)
Trimer: 5-15% (weight)
Tetramer: 5-15% (weight)
Pentamer: 5-15% (weight)
Hexamer: 5-15% (weight)
Haptamer: 5-15% (weight)
Octamer: 1-10% (weight)
Oligomer: add to 100% (weight)
In a special embodiment of the present invention, use the industrial Castor Oil Fatty Acid mixture of forming by castor oil acid of hydroxy stearic acid and castor oil acid or as many as 90% (weight), its weight ratio is 99: 1 to 1: 99, preferred 75: 25 to 10: 90.Also can be in the same way dehydroamino acid separately, then mix the gained condensation product.Polyalcohol component such as polyglycereol and multi-hydroxy stearic acid or poly castor oil acid mixture with after-condensation in, form a kind of complex mixture of even polyester.One, two, three relevant with raw materials used ratio in polyalcohol multi-hydroxy stearic acid ester of the present invention and the preferred polyglycereol multi-hydroxy stearic acid ester with the content of oligoester.One of the inventive method preferred embodiment in, carry out from condensation with about 1000kg12-hydroxy stearic acid, up to the product that to generate a kind of acid number scope be 50-55, polyglycereol with the above-mentioned composition of about 150kg carries out esterification then, till acid number is reduced to less than 2, obtained a kind of polyalcohol multi-hydroxy stearic acid ester with particularly advantageous commercial Application character.Condensation product based on polyglycereol and multi-hydroxy stearic acid or multi-hydroxy stearic acid/poly castor oil acid can be characterized by its iodine number.Typical example is iodine number<10 (the 12-hydroxy stearic acid based on 100%) or is the polyester of 65-80 (based on 90%12-hydroxy stearic acid and 10% castor oil acid).Polyalcohol
The suitable polyalcohol of considering as the additional ingredients of the new emulsifying agent of the present invention has 2-15 carbon atom and at least 2 oh groups.Typical example has
Glycerine;
Alkylene dihydric alcohol is ethylene glycol, diethylene glycol, propane diols, polyethylene glycol or polypropylene glycol for example, and its molecular weight ranges is 100-1000 dalton;
From condensation degree is the industrial oligomeric glycerol mixture of 1.5-10, and for example two glycerol contents are industry two glycerol mixtures of 4050% (weight);
Methylol compound is as particularly trimethylolethane, trimethylolpropane, tri hydroxy methyl butane, pentaerythrite and dipentaerythritol;
The low alkyl group glucoside particularly has the glucoside of 1-8 carbon atom, for example methyl and butyl glucoside at alkyl;
The sugar alcohol of 5-12 carbon atom, for example D-sorbite or mannitol;
The sugar of 5-12 carbon atom, for example glucose or sucrose;
Amino sugar is aminoglucose for example.
Polyalcohol, preferably glycerine, the content in new oil-water emulsifiers can be the 5-30% of emulsifying agent weight, preferred 15-25%.
Industrial applicibility
New oil-water emulsifiers is particularly suitable for the emulsion of preparation temperature and storage-stable, and irrelevant with the polarity of the oily component for the treatment of emulsification.Preparation has gratifying full-bodied emulsion particularly also can to use the very strong oil of polarity to come rapidly and reliably.
Another theme of the present invention relates to and is used for preparing for example new oil-water emulsifiers of ointment, lotion, emollient etc. of cosmetics and/or pharmaceutical preparation.
The emulsion of using oil-water emulsifiers of the present invention and obtaining can also contain other auxiliary agent and additive, for example surfactant, oil body, assistant for emulsifying agent, rich ester agent, grease, wax, stabilizing agent, biochemical, anticorrisive agent, pigment and spices.
Emulsion can contain the surfactant compatible with other composition.Typical example is fatty alcohol polyglycol ether sulfate, sulfuric acid monoglyceride, one and/or dialkyl group sulfo-succinate, aliphatic acid isethionate, aliphatic acid sarcosinate, aliphatic acid taurate (tauride), ether carboxylic acid, alkyl amino betaine and/or vegetable protein aliphatic acid condensation product.
As oil body, for example can be based on 6-18, Guerbet alcohol, the straight chain C of the fatty alcohol of preferred 8-10 carbon atom 6-C 20-aliphatic acid and straight chain C 6-C 20The ester of-fatty alcohol, side chain C 6-C 13-carboxylic acid and straight chain C 6-C 20The ester of-fatty alcohol, straight chain C 6-C 18-aliphatic acid and branched-chain alcoho particularly the aliphatic acid of ester, straight chain and/or the side chain of 2-Ethylhexyl Alcohol and polyalcohol (for example dimer diol or three polyglycols) and/or Guerbet alcohol ester, based on C 6-C 10The primary alconol of the glyceryl ester of-aliphatic acid, vegetable oil, side chain, the cyclohexane of replacement, Guerbet carbonic ester, dialkyl ether and/or aliphatic series or alicyclic.
As assistant for emulsifying agent, can use nonionic, both sexes and/or zwitterionic interfacial activity compound, it is characterized in that having the preferred of a lipophilic is straight chained alkyl or kiki alkenyl group and at least one hydrophilic radical.Hydrophilic radical both can be that ionic group also can be a non-ionic group.
Nonionic emulsifier contains, and for example, the combination of polyalcohol group, multi alkylidene diol ether group or polyalcohol and multi alkylidene diol ether group is as hydrophilic radical.Preferably contain non-ionic surface active agent at least a in the following groups as oil-water emulsifiers: (a1) 2-30Mol oxirane and/or 0-5Mol expoxy propane are on the straight-chain fatty alcohol of 8-22 carbon atom, on the aliphatic acid of 12-22 carbon atom and addition product on the alkyl phenol of 8-15 carbon atom arranged at alkyl; (a2) C of the addition product of 1-30Mol oxirane on glycerine 12/18-fatty-acid monoester and diester; (a3) the monoglyceride diester of the saturated and unrighted acid of 6-22 carbon atom and sorbitan monoesters and diester and its ethylene oxide adduct; (a4) the ethoxyquin alkyl monoglycosides and the oligoglycosides of 8-22 carbon atom are arranged at alkyl; (a5) addition product of 15-60Mol oxirane on the castor oil of castor oil and/or hydrogenation.The same suitable mixture that also has multiple material in these materials.Oxirane and/or expoxy propane are at the monoglyceride of fatty alcohol, aliphatic acid, alkyl phenol, aliphatic acid and the addition product on diester and sorbitan monoesters and the diester, and perhaps the addition product on castor oil all is known commercially available prod.They are homologue mixtures, and its average degree of alkoxylation is equivalent to the amount of material ratio of the matrix that oxirane and/or expoxy propane and addition reaction carry out.The C of the addition product of oxirane on glycerine 12/18-fatty-acid monoester and diester in DE-PS2024051 as cosmetics to return the fat agent open.In addition, can also use zwitterionic surfactant as emulsifying agent.Zwitterionic surfactant represents that those contain the surface active cpd of at least one quaternary ammonium group and at least one carboxylate groups and a sulfonate groups in molecule.Specially suitable zwitterionic surfactant is alleged betaine such as N-alkyl N-; N-dimethylglycine ammonium; coconut alkyl-dimethylglycine ammonium for example; N-acyl amino propyl group-N; N-dimethylglycine ammonium; coconut acyl amino propyl-dimethyl glycine ammonium and the 2-alkyl-3-carboxymethyl-3-hydroxyethyl imidazole quinoline and the coconut acyl amino ethyl-hydroxyethyl carboxymethyl glycinate of 8-18 carbon atom are arranged at alkyl or acyl group for example.Particularly preferably be known fatty acid amide derivant with the coconut monoethanolamide CAB (Cocoamido propyl Betaine) of CTFA-name.Same suitable emulsifying agent is an amphoteric surfactant.Amphoteric surfactant be meant those in molecule except C 8/18-alkyl or carboxyl groups also contain outward at least one free amino group and at least one-COOH-or-SO 3The H-group also can form the surface active cpd of inner salt.Suitable examples of amphoteric surfactants is N-alkyl glycine, N-alkyl propionic acid, N-alkyl amino butyric acid, N-alkyl imino dipropionic acid, N-hydroxyl-ethyl-N-alkylamide propyl glycine, N-alkyl Taurine, N-alkyl methyl amimoacetic acid, 2-alkyl aminopropionic acid and p dialkylaminobenzoic acid, and its moieties all has 8-18 carbon atom.Particularly preferred amphoteric surfactant is N-coconut alkyl aminopropionic acid salt, coconut acyl amino ethylamino propionate and C 12/18-acyl group methyl amimoacetic acid.
As the operable material of rich ester agent, for example, be lanolin derivative, lecithin derivative, polyol fatty acid ester, single glycerine and the Marlamid of many ethyoxyls, wherein latter's stabilizer function that can spume simultaneously.The representative instance of grease is a glyceride, and wax can be considered beeswax, paraffin or microwax (Mikrowachse), combines with hydrophilic wax in case of necessity, for example cetyl stearyl alcohol and/or palmitic acid or stearic partial glyceride.Can use the slaine of aliphatic acid, for example dolomol, aluminum stearate and/or zinc stearate as stabilizing agent.Bioactivator is meant, for example, and plant extraction liquid and vitamin compound.Anticorrisive agent can use for example phenoxetol, formalin, metagin (Parabene), pentanediol or sorb saccharic acid.Pearling agent for example can be considered dihydroxylic alcohols distearate such as glycol distearate, also can use aliphatic acid monoethylene glycol ester.Dyestuff can use and be suitable for cosmetics and reliable material, for example at public publication " Kosmetische Faerbemittel ", and the dyestuff committee of German scientific research association, chemical publishing house, Weinheim, 1984, those that the 81-106 page or leaf is listed.These dyestuffs use with the concentration of the 0.001-0.1% of total mixture weight usually.
With goods is benchmark, and the total content of auxiliary agent and additive can account for 1-50, preferred 5-40% (weight).The preparation of goods can be common mode carry out, that is to say, for example finish by heat, hot and cold-hot/cold or PIT emulsification.Here relate to pure mechanical means, chemical reaction does not take place.
EXAMPLE Example 1-9
The operating weight ratio is the C of 60: 40 (embodiment R1-R5) or 40: 60 (embodiment R6-R9) 12/14-coconut alkyl oligoglycosides (Plantaren APG 1200, Henkel KGaA, Duesseldorf/FRG) and polyglycereol many-mixture of 12-hydroxy stearic acid ester (Dehymuls PGPH, Henkel KGaA) and obtain 9 kinds of Example formulations.I is evenly stirred at 20 ℃, II is under agitation slowly added mutually, then III is stirred adding mutually, evenly mix, mix mutually with IV at last.In hot preparation (method B), I heat phase to 85 ℃, and evenly stirring is added to the II of preheating, then makes the emulsion cooling.The composition of emulsion is as shown in table 1:
The composition of table 1 Example formulations
Phase Component (CTFA) Example formulations (weight %)
???R1 ???R2 ???R3 ???R4 ???R5 ???R6 ???R7 ???R8 ???R9
??I Oil-water emulsifiers ???2.9 ??2.4 ??2.4 ??3.1 ??4.0 ??6.4 ??6.4 ??6.4 ??3.3
The PEG-20 tristerin ???- ??1.6 ??1.6 ??- ??- ??- ??- ??- ??-
NaLS ???- ??- ??- ??2.3 ??- ??- ??- ??- ??-
Glycerine (99%) ???- ??- ??- ??- ??- ??4.0 ??- ??4.0 ??-
Propane diols ???- ??- ??- ??- ??- ??- ??4.0 ??- ??-
16 aryl alcohols (cetearyl) ???- ??- ??- ??- ??- ??- ??- ??5.5 ??-
The octyl-decyl glyceryl ester ??16.0 ??16.0 ??- ??16.0 ??- ??16.0 ??16.0 ??16.0 ??16.0
Paraffin oil, the dilute liquid shape ??- ??- ??16.0 ??- ??16.0 ??- ??- ??- ??-
??II Distilled water Add to 100
Glycerine (99%) ??3.0 ??3.0 ??3.0 ??3.0 ??3.0 ??- ??- ??- ??3.0
Salt ??- ??- ??- ??- ??- ??- ??- ??5.0
??III Polymer Carbopol 980(2%) ??15.0 ??15.0 ??15.0 ??15.0 ??15.0 ??15.0 ??15.0 ??- ??-
??Keltrol BT ??- ??- ??- ??- ??- ??- ??- ??- ??1.5
??IV Potassium hydroxide (20%) ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??0.5 ??- ??0.5
The pH value ??6.6
Viscosity *[Pas] ??18 ??39 ??> ??40 ??12 ??11 ??24 ??24 ??8 ??14
The preparation method ??A ??A ??A ??A ??A ??A ??A ?B ??A
Obtained stable in storage emulsion, its range of viscosities of pressing that Brookfield (RVF, 23 ℃, 10UpM, rotor 5 or 6 is in embodiment R3) measures is 5-50000mPas.Embodiment 10-13, Comparative Examples V1 and V2
Preparation contains the mixture of 20% (weight) almond oil, 7% (weight) emulsifying agent, 5% (weight) glycerine (86% weight) and 5% (weight) magnesium sulfate-7-hydrate (water adds to 100% (weight)), places 4 time-of-weeks, measures viscosity.Tested following emulsifying agent:
A1)Plantaren APG?1200/Dehymuls PGPH=60∶40
A2)plantaren APG?1200/Dehymuls PGPH=40∶60
A3) Plantaren APG 1200/Dehymuls PGPH/ glycerine=25: 50: 25
A4) laurate-N-methyl glucose amide/Dehymuls PGPH=60: 40
B1) polyglycereol polyricinoleate
B2) glycerine-poly--12-hydroxy stearic acid ester the results are shown in the table 2:
Table 2 contains the viscosity and the stability of the emulsion of polarity oil body
Embodiment Viscosity behind the certain hour [mPas] Stability behind the certain hour
Emulsifying agent 1 day 1 week 4 weeks 1 day 4 weeks
?10)A1 ??24000 ???23000 ???23000 Stable Stable
?11)A2 ??23500 ???22000 ???20000 Stable Stable
?12)?A3 ??19500 ???19000 ???19000 Stable Stable
?13)A4 ??25000 ???24000 ???23500 Stable Stable
?V1)B1 ??- ???- ???- Not emulsification
?V2)B2 ??- ???- ???- Not emulsification
Embodiment 14 and 15, Comparative Examples V3 and V4
Two kinds of emulsions have been prepared with emulsifier mixture of the present invention and a kind of control mixture of forming by Ceteareth-12 and Ceteareth-20 that contains oxirane according to hot method.Measure the viscosity of emulsion as mentioned above with the Brookfield method, and place 1 day to 8 weeks.In room temperature or 40 ℃ of following 4 or 8 its stability of all post-evaluations of placing.R10 and R12 preparation are of the present invention, and R11 and R13 preparation are used for contrast.The results are shown in the table 3.
The viscosity of table 3 emulsion and stability
Component (CTFA-name) Example formulations (weight %)
??R10 ??R11 ??R12 ??R13
The emulsifying agent compound ??6.6 ??- ??- ??-
The decyl polydextrose ??- ??- ??2.4 ??-
Polyglyceryl is many-the 12-hydroxy stearic acid ester ??- ??- ??1.2 ??-
??Ceteareth-12 ??- ??1.5 ??- ??1.5
??Ceteareth-20 ??- ??1.5 ??- ??1.5
Hydrogenated palm glyceride ??- ??- ??8.0 ??8.0
The oil base eruciate ??- ??- ??2.0 ??2.0
Ceraphyl 140 ??- ??- ??4.0 ??4.0
Dioctyl ether ??- ??- ??2.0 ??2.0
Octyl group/decyl glyceryl ester ??- ??- ??4.0 ??4.0
The glyceryl stearate ??15.0 ??15.0 ??- ??-
Paraffin oil, the liquid of dilution ??10.0 ??10.0 ??- ??-
Polymer Carbopol 980 ??- ??- ??10.0 ??10.0
KOH, 20% (weight) ??- ??- ??0.4 ??0.4
Glycerine ??- ??3.0 ??3.0 ??3.0
Water, anticorrisive agent Add to 100% (weight)
Viscosity behind the certain hour [mPas]
-2 days ??775000 ??300000 ??200000 ??112500
-1 week ??750000 ??287500 ??187000 ??93750
-4 weeks ??737500 ??200000 ??200000 ??75000
-8 weeks ??750000 ??150000
Stability behind the certain hour
-4 weeks (room temperature) Stable Stable Stable Stable
-4 weeks (40 ℃) Stable Stable Stable Stable
-8 weeks (room temperature) Stable Stable
-8 weeks (40 ℃) Stable Stable
*) the emulsifying agent compound: 18% (weight) polyglyceryl is many-the 12-hydroxy stearic acid ester
36% (weight) decyl polydextrose
46% (weight) glycerine

Claims (9)

1. oil-water emulsifiers contains
A1) alkyl and/or alkenyl oligoglycosides,
A2) aliphatic acid-N-alkyl polyhydroxy alkylamide and/or
A3) acyl glutamic acid ester
B) polyalcohol multi-hydroxy stearic acid ester,
Wherein condition is, a): weight ratio scope b) is 90: 10 to 10: 90.
2. according to the described oil-water emulsifiers of claim 1, it is characterized in that it contains the alkyl and/or the alkenyl oligoglycosides of formula (I),
R 1O-[G] p(I) R in the formula 1Expression contains the alkyl and/or the alkenyl of 4-22 carbon atom, and G represents to contain the glycosyl of 5 or 6 carbon atoms, and p is numerical value 1-10.
3. according to claim 1 and 2 described oil-water emulsifiers, it is characterized in that it contains the aliphatic acid-N-alkyl polyhydroxy alkylamide of formula (II), R in the formula 2CO represents the aliphatic acyl of 6-22 carbon atom, R 3The alkyl or the hydroxy alkyl of expression hydrogen, a 1-4 carbon atom, [Z] expression contains the polyhydroxy alkyl of the straight or branched of 3-12 carbon atom and 3-10 hydroxyl.
4 according to the described oil-water emulsifiers of claim 1-3, it is characterized in that it contains the acyl glutamic acid ester of formula (IV),
Figure A9619688600022
COR in the formula 4Expression contains the acyl group of the straight or branched of 6-22 carbon atom and 0 and/or 1,2 or 3 two key, and X represents hydrogen, alkali metal and or alkaline-earth metal, ammonium, alkylammonium, alkanol ammonium or glucose ammonium.
5. according to the described oil-water emulsifiers of claim 1-4, it is characterized in that, it contain polyglycereol many-the 12-hydroxy stearic acid ester.
6. according to the described oil-water emulsifiers of claim 1-5, it is characterized in that contained component sugar surfactant and formula b a)) the weight ratio of polymer be 70: 30 to 30: 70.
7. according to the described oil-water emulsifiers of claim 1-6, it is characterized in that it contains polyalcohol as other component.
8. according to the described oil-water emulsifiers of claim 7, it is characterized in that, is benchmark with the weight of emulsifying agent, contains the polyalcohol of 5-30% weight.
9. the application of the described oil-water emulsifiers of claim 1 aspect preparation cosmetics and/or pharmaceutical preparation.
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US9593038B2 (en) 2009-08-03 2017-03-14 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
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US10377663B2 (en) 2009-08-03 2019-08-13 Ppg Industries Ohio, Inc. Methods to make glass compositions and fibers made therefrom
US10487007B2 (en) 2009-08-03 2019-11-26 Ppg Industries Ohio, Inc. Glass compositions and fibers made therefrom
CN111170883A (en) * 2020-01-06 2020-05-19 岳阳科罗德联合化学工业有限公司 Fatty acyl amino acid polyhydroxy ester compound and preparation method thereof

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JP3933202B2 (en) 2007-06-20
JPH11512334A (en) 1999-10-26
DE59609134D1 (en) 2002-05-29
AU6986096A (en) 1997-04-01
ES2175125T3 (en) 2002-11-16
EP0853494B1 (en) 2002-04-24
EP0853494A1 (en) 1998-07-22
US6264961B1 (en) 2001-07-24
ATE216630T1 (en) 2002-05-15
KR19990028692A (en) 1999-04-15
AU704033B2 (en) 1999-04-15
CN1092995C (en) 2002-10-23
DE19533539A1 (en) 1997-03-13
WO1997010049A1 (en) 1997-03-20

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